EP1083776A1 - Organische elektrolumineszente vorrichtung und verfahren zu ihrer herstellung - Google Patents

Organische elektrolumineszente vorrichtung und verfahren zu ihrer herstellung Download PDF

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EP1083776A1
EP1083776A1 EP00902980A EP00902980A EP1083776A1 EP 1083776 A1 EP1083776 A1 EP 1083776A1 EP 00902980 A EP00902980 A EP 00902980A EP 00902980 A EP00902980 A EP 00902980A EP 1083776 A1 EP1083776 A1 EP 1083776A1
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Prior art keywords
group
layer
organic
inorganic thin
organic light
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French (fr)
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EP1083776A4 (de
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Hisayuki Kawamura
Hiroaki Nakamura
Chishio Hosokawa
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Idemitsu Kosan Co Ltd
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Idemitsu Kosan Co Ltd
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Priority claimed from JP11036420A external-priority patent/JP2000235893A/ja
Priority claimed from JP13499799A external-priority patent/JP4673947B2/ja
Application filed by Idemitsu Kosan Co Ltd filed Critical Idemitsu Kosan Co Ltd
Publication of EP1083776A1 publication Critical patent/EP1083776A1/de
Publication of EP1083776A4 publication Critical patent/EP1083776A4/de
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/17—Carrier injection layers
    • H10K50/171—Electron injection layers
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/22—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of auxiliary dielectric or reflective layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/17—Carrier injection layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/805—Electrodes
    • H10K50/81—Anodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/805—Electrodes
    • H10K50/82—Cathodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension

Definitions

  • the present invention relates to an organic electroluminescent device (hereinafter may be called "organic EL device”) and a method of manufacturing the organic EL device. More particularly, the present invention relates to an organic EL device suitably used for display apparatuses for home use or industrial use, light sources for printer heads, and the like, and to a method of manufacturing the organic EL devices.
  • organic EL device suitably used for display apparatuses for home use or industrial use, light sources for printer heads, and the like, and to a method of manufacturing the organic EL devices.
  • the organic light-emitting layer is an organic substance, injecting electrons from a cathode layer is not easy.
  • the organic substance generally can transfer electrons and positive holes only with difficulty, the organic light-emitting layer tends to deteriorate easily and produce leakage current when used for a long period of time.
  • Japanese Patent Application Laid-open No. 8-288069 discloses an organic EL device provided with an insulating thin layer between an electrode and an organic light-emitting layer as a means for extending the life of the organic EL device.
  • the organic EL device disclosed in this patent application has a configuration in which an insulating thin layer of aluminum nitride, tantalum nitride, or the like is provided between an anode layer and an organic light-emitting layer or between a cathode layer and an organic light-emitting layer.
  • U.S. Patent No. 5,853,905 discloses an organic EL device provided with an insulating thin layer between an anode layer and a light-emitting layer or a cathode layer and a light-emitting layer.
  • the US. Patent also discloses SiO 2 , MgO, and Al 2 O 3 as materials for forming the insulating thin layers.
  • Japanese Patent Application Laid-open No. 9-260063 discloses an organic EL device having an inorganic material layer comprising NiO and at least one compound selected from the group consisting of In 2 O 3 , ZnO, SnO 2 , and compounds containing B, P, C, N, or O, or an inorganic material layer of Ni 1-x O (0.05 ⁇ x ⁇ 0.5) between an electrode and an organic light-emitting layer.
  • Japanese Patent No. 2824411 discloses an organic EL device having an anode layer made of a conductive metal oxide material exhibiting a work function greater than indium tin oxide (ITO) such as RuO x , MoO 3 , and V 2 O 5 , for example.
  • ITO indium tin oxide
  • This Japanese Patent proposes in the specification an anode layer having a two layer structure consisting of these conductive metal oxide materials and an ITO to improve the light transmittance.
  • the inorganic compounds such as aluminum nitride, tantalum nitride, SiO 2 , and the like used as an insulating thin layer in the organic EL devices disclosed in Japanese Patent Application Laid-open No. 8-288069 and U.S. Patent No. 5,853,905 have a great ionization potential which results in an increased driving voltage.
  • the inorganic thin layers consisting of these inorganic compounds are electric insulating layers having an excessively large ionization energy, positive holes are injected from the anode layer by a tunnel effect. Therefore, a high driving voltage is required between the electrodes of the organic EL device to obtain a desired luminous brightness.
  • the organic EL device disclosed in Japanese Patent Application Laid-open No. 9-260063 is characterized by the use of NiO as a major component, which unduly limits the types of materials usable as an inorganic material layer and exhibits only a low luminous efficiency.
  • the organic EL device disclosed in Japanese Patent No. 282411 has the problems of small positive hole mobility and insufficient durability in spite of the use of the metal oxide materials such as RuO x (1 ⁇ x ⁇ 2), MoO 3 , and V 2 O 5 .
  • the metal oxide materials such as RuO x (1 ⁇ x ⁇ 2), MoO 3 , and V 2 O 5 exhibit a large optical absorption coefficient of 27,000 cm -1 or more, giving rise to remarkable coloration. Therefore, the light transmittance in the visible radiation range of the anode layer made of these metal oxide materials is very low, for example, about 1/9 to 1/5 that of ITO, giving rise to problems such as a poor luminous efficiency and a small quantity of light which can be emitted.
  • anode layer with a two-layer structure consisting of lamination of a thin film of these metal oxide materials and ITO exhibits only a small light transmittance (about 1/2 that of ITO).
  • Such an anode layer cannot be used in practice.
  • the thickness of the ITO and a metal oxide film must be restricted within a prescribed range, resulting in a limitation in the manufacturing process.
  • an intermediate level for injection of electric charges can be formed in the inorganic thin layer by forming the inorganic thin layer from a combination of several specific inorganic compounds.
  • the inventors have further found that the combined use of specific inorganic compounds for forming the inorganic thin layer may produce an organic EL device with excellent transparency and durability, and superior luminous brightness at a low applied voltage (for example, less than DC 10V).
  • an object of the present invention is to provide an organic EL device having a specific inorganic thin layer and exhibiting excellent durability, a low driving voltage, and superior luminous brightness, as well as a method of efficiently manufacturing such an organic EL device.
  • Another object is to provide an organic EL device having an electrode layer made from a combination of specific inorganic compounds and exhibiting excellent durability, a low driving voltage, and superior luminous brightness, as well as a method of efficiently manufacturing such an organic EL device.
  • Figure 1 shows a sectional view of an organic EL device 102 formed by successively laminating an anode layer 10, an inorganic thin layer 12, an organic light-emitting layer 14, and a cathode layer 16 on a substrate (not shown in the drawing).
  • the first embodiment will now be explained focusing on the inorganic thin layer 12 and the organic light-emitting layer 14 which are characteristic in the first embodiment. Therefore, configurations and methods of manufacture of other components such as, for example, the anode layer 10 and cathode layer 16 are only briefly explained, and conventionally known configurations and methods of manufacture in the field of organic EL devices can be applied to the other parts which are not mentioned here.
  • the first and second inorganic thin layers (hereinafter may be simply referred to as "inorganic thin layer") must comprise the inorganic compounds of the following group A and group B in combination.
  • inorganic compounds of group A are SiO x (1 ⁇ x ⁇ 2), GeO x (1 ⁇ x ⁇ 2), SnO 2 , PbO, In 2 O 3 , ZnO, GaO, CdO, MgO, SiN, GaN, ZnS, ZnSe, CdS, CdSe, ZnSSe, CaSSe, MgSSe, GaInN, LiO x (1 ⁇ x ⁇ 2), SrO, CsO x , (1 ⁇ x ⁇ 2), CaO, NaO x (1 ⁇ x ⁇ 2), mixtures of these inorganic compounds, and laminates of these inorganic compounds.
  • a chalcogenide of Si, Ge, Sn, Zn, Cd, Mg, Ba, K, Li, Na, Ca, Sr, Cs, or Rb, and a nitride thereof are preferable.
  • Preferable inorganic compounds of group A are chalcogenide compounds of Si, Ge, Sn, Zn, Cd, Mg, Al, Ba, K, Li, Na, Ca, Sr, Cs, or Rb, and particularly oxides thereof.
  • group B is RuO x (1 ⁇ x ⁇ 2), V 2 O 5 , MoO 3 , Ir 2 O 3 , NiO 2 , RhO 4 , ReO x (1 ⁇ x ⁇ 2), CrO 3 , Cr 2 O 3 , RhO x (1 ⁇ x ⁇ 2), MoO x (1 ⁇ x ⁇ 2), and VO x (1 ⁇ x ⁇ 2). These compounds may be used either individually or in combinations of two or more.
  • oxides of Ru, Re, V, Mo, Pd, and Ir specifically, RuO x (1 ⁇ x ⁇ 2), ReO x (1 ⁇ x ⁇ 2), V 2 O 5 , MoO 3 , MoO x (1 ⁇ x ⁇ 2), PdO 2 , and Ir 2 O 3 are preferable.
  • the use of these group B ensures formation of an intermediate level in the inorganic thin layer, allowing easy injection of electric charges.
  • the content of the group B is preferably in the range of 0.1 to 50 atomic % for 100 atomic % of the total of the inorganic thin layer.
  • an intermediate level may not be formed in the inorganic thin layer; if more than 50 atomic %, the inorganic thin layer may be colored or the transparency (light transmittance) may be impaired.
  • the content of the group B is more preferably in the range of 1 to 30 atomic %, and most preferably 2 to 20 atomic %, for 100 atomic % of the total of the inorganic thin layer.
  • the content of the group A is equivalent to the total amount (100 atomic %) minus the content of the group B. Therefore, when the content of the group B is in the range of 0. 1 to 50 atomic %, the content of the group A is in the range of 50 to 99.9 atomic %.
  • a compound other than the group A or the group B a third component
  • the thickness of the inorganic thin layer is not specifically restricted, such a thickness is preferably in the range of 0.5 to 100 nm. If the thickness of the inorganic thin layer is less than 0.5 nm, pin-holes may be produced and a leakage current may be observed when the layer is used for a long time; if more than 100 nm, on the other hand, the driving voltage may increase and luminous brightness may decline.
  • the thickness of the inorganic thin layer is in the range of 0.5 to 50 nm, and preferably 0.5 to 5 nm.
  • a sputtering method vapor deposition method, spin coat method, casting method, LB method (Langmuir-Blodgett method), and the like may be employed.
  • a radio frequency magnetron sputtering method is particularly preferred.
  • the radio frequency magnetron sputtering method it is desirable to perform sputtering in an inert gas under vacuum of 1 ⁇ 10 -7 to 1 ⁇ 10 -3 Pa, a layer forming speed of 0.01 to 50 nm/second, and a substrate temperature of -50°C to 300°C.
  • a conventional organic EL device having an inorganic thin layer consisting of AlN, TaN, and the like has a problem of requiring a high driving voltage because of utilization of a tunnel effect.
  • an intermediate level is provided in the inorganic thin layer in the present invention to enable the organic EL device to be driven at a low voltage and to exhibit high luminous brightness. More specifically, by forming an inorganic thin layer from the inorganic compounds of group A and group B, the energy level of the inorganic thin layer is maintained between the energy level of the electrode layer (anode layer, or cathode layer) and the energy level of the organic light-emitting layer. Electric charges are injected through the intermediate level (Ei) thus formed. Because electric charges are easily injected into an organic light-emitting layer in this manner, not only may the organic EL device be driven at a low voltage, but it also exhibits high luminous brightness. In addition, durability of the organic EL device is remarkably improved due to the low driving voltage.
  • the intermediate level (Ei) in the inorganic thin layer may exist either inside the inorganic thin layer or in the interface of the inorganic thin layer and the organic light-emitting layer.
  • the energy level (Ec) of the inorganic thin layer is set at a value smaller than the work function of the anode layer(Wa), to prevent electrons from passing through the organic light-emitting layer.
  • Ec energy level of the inorganic thin layer
  • the energy level (Ev) of the inorganic thin layer is desirable to set the energy level (Ev) of the inorganic thin layer greater than the work function of the cathode layer(Wc), so that positive holes may not pass through the organic light-emitting layer.
  • Ev energy level of the inorganic thin layer
  • the organic light-emitting material used as a material for the organic light-emitting layer preferably has the following three functions at the same time.
  • the material does not necessarily possess all of the functions (a) to (c). Some material which exhibits more excellent positive hole injecting and transporting characteristics than electron injecting and transporting characteristics, for example, is suitable as an organic luminescent material. Therefore, a material which may accelerate the movement of electrons in the organic light-emitting layer and may cause the electrons to recombine with positive holes around the center of the organic light-emitting layer is suitably used.
  • the electron mobility of the organic light-emitting material is preferably 1 ⁇ 10 -7 cm 2 /V ⁇ s or more. If less than 1 ⁇ 10 -7 cm 2 /V ⁇ s, a high-speed response in the organic EL device may become difficult and the luminous brightness may decline.
  • the electron mobility of the organic light-emitting material is more preferably in the range of 1 ⁇ 10 -7 to 2 ⁇ 10 -3 cm 2 /V ⁇ s, and particularly preferably 1.2 ⁇ 10 -7 to 1.0 ⁇ 10 -3 cm 2 /V ⁇ s.
  • the reason for restricting the electron mobility to a value smaller than the positive hole mobility of the organic light-emitting material in the organic light-emitting layer is that otherwise not only the organic light-emitting materials usable for the organic light-emitting layer may be unduly limited, but also luminous brightness may decline.
  • the electron mobility of the organic light-emitting material is preferably greater than 1/1,000 of the positive hole mobility. The reason is that if the electron mobility is excessively small, it may be difficult for the electrons to recombine with positive holes around the center of the organic light-emitting layer and the luminous brightness may decline.
  • the relationship between the positive hole mobility ( ⁇ h ) and the electron mobility ( ⁇ e ) of the organic light-emitting material in the organic light-emitting layer should preferably satisfy the inequality of ⁇ h/2 > ⁇ c > ⁇ h /500, and more preferably of ⁇ h /3 > ⁇ c > ⁇ h /100.
  • the organic light-emitting layer contain one or more aromatic compounds having a styryl group represented by the following formulas (1) to (3) described above (such an aromatic compound may be called "a styryl group-containing aromatic compound").
  • aromatic compounds having a styryl group represented by the following formulas (1) to (3) described above such an aromatic compound may be called "a styryl group-containing aromatic compound”.
  • the above-mentioned conditions for the electron mobility and the positive hole mobility of the organic light-emitting material in the organic light-emitting layer may be easily satisfied by using such a styryl group-containing aromatic compound.
  • arylene groups having 5 to 50 nucleus atom numbers phenylene, naphthylene, anthranylene, phenanthrylene, pyrenylene, cholonylene, biphenylene, terphenylene, pyrrolylene, furanylene, thiophenylene, benzothiophenylene, oxadiazolylene, diphenylanthranylene, indolylene, carbazolylene, pyridylene, benzoquinolylene, and the like may be given.
  • the aromatic group having 6 to 50 carbon atoms may have a substituent.
  • substituents are alkyl groups having 1 to 6 carbon atoms such as an ethyl group, methyl group, i-propyl group, n-propyl group, s-butyl group, t-butyl group, pentyl group, hexyl group, cyclopentyl group, and cyclohexyl group; alkoxy groups having 1 to 6 carbon atoms such as an ethoxy group, methoxy group, i-propoxy group, n-propoxy group, s-butoxy group, t-butoxy group, pentoxy group, hexyloxy group, cyclopentoxy group, and cyclohexyloxy group; aryl groups having 5 to 50 nucleus atom numbers, amino groups substituted by an aryl group having 5 to 50 nucleus atom numbers, ester groups substituted by an aryl group having 5 to 50 nucleus atom
  • the organic light-emitting layer may further comprise other compounds.
  • Such other compounds include fluorescent whitening agents such as benzothiazoles, benzoimidazoles, benzooxazoles, and the like; styrylbenzene compounds; and metal complexes having an 8-quinolinol derivative as a ligand which are typified by Alq of the following formula (45).
  • an organic light-emitting material having a distyrylarylene skeleton for example, a material prepared by reacting a host substance such as 4,4'-bis(2,2-diphenylvinyl)biphenyl, and a strong fluorescent dye with a color from blue to red, such as a cumarin-based fluorescent dye, or a material doping other fluorescent dye having a similar color to the host substance, may be suitably used together.
  • a host substance such as 4,4'-bis(2,2-diphenylvinyl)biphenyl
  • a strong fluorescent dye with a color from blue to red such as a cumarin-based fluorescent dye, or a material doping other fluorescent dye having a similar color to the host substance
  • vacuum deposition is preferably performed at a vacuum deposition temperature of 50 to 450°C in an inert gas, under vacuum of 1 ⁇ 10 -7 to 1 ⁇ 10 -3 Pa, a layer forming speed of 0.01 to 50 nm/second, and a substrate temperature of -50°C to 300°C.
  • the organic light-emitting layer may be also formed by dissolving a binding agent and an organic light-emitting material in a solvent to obtain a solution and by spin-coating the solution to form a thin layer.
  • the organic light-emitting layer is preferably a thin layer formed by deposition of a gaseous material by suitably selecting layer-forming methods and conditions, or a molecular deposition layer made by solidification of raw material compounds which are in the form of a solution or a liquid.
  • a molecular deposition layer can be distinguished from a thin layer (molecular accumulation layer) formed by the LB method by the differences of aggregation structure and high dimensional structure as well as by the functional differences thereof.
  • the thickness of the organic light-emitting layer is not specifically limited and may be appropriately selected according to the conditions. Preferably, the thickness is in the range of 5 nm to 5 ⁇ m. If the thickness of the organic light-emitting layer is less than 5 nm, luminous brightness and durability may be impaired; if more than 5 ⁇ m, on the other hand, the applied voltage may increase.
  • the thickness of the organic light-emitting layer is preferably in the range of 10 nm to 3 ⁇ m, and more preferably 20 nm to 1 ⁇ m.
  • metals, alloys, electrically conductive compounds with a large work function for example, 4 eV or more
  • a large work function for example, 4 eV or more
  • ITO indium tin oxide
  • indium, copper, tin, zinc oxide, gold, platinum, palladium, carbon, and the like may be used either individually or in combinations of two or more.
  • the thickness of the anode layer is not specifically restricted, such a thickness is preferably in the range of 10 to 1,000 nm, and more preferably 10 to 200 nm.
  • the anode layer should be substantially transparent. Specifically, the anode layer has light transmittance of 10% or more, and preferably 70% or more.
  • metals, alloys, electric conductive compounds with a small work function for example, less than 4 eV
  • magnesium, aluminum, indium, lithium, sodium, cesium, silver, and the like may be used either individually or in combination of two or more.
  • the thickness of the cathode layer is not specifically restricted, such a thickness is preferably in the range of 10 to 1,000 nm, and more preferably 10 to 200 nm.
  • the following materials (a) to (h) may be given as examples of a material preferably used as a sealing layer.
  • a vacuum deposition method, spin coat method, sputtering method, cast method, MBE (molecular beam epitaxy) method, cluster ion beam vapor deposition method, ion plating method, plasma polymerization method (radio frequency exciting ion plating method), plasma CVD (Chemical Vapor Deposition) method, laser CVD method, heat CVD method, gas source CVD method, and the like may be appropriately used for forming the sealing layer.
  • the second embodiment is an organic EL device 102, which is the same as the above-mentioned first embodiment shown in Figure 1, except for an improvement in the anode layer 10.
  • the second embodiment will now be explained focusing on the anode layer 10 which is characteristic in the second embodiment. Therefore, configurations and methods of manufacture of other components such as, for example, the organic light-emitting layer 14 and the like are only briefly explained, and conventionally known configurations and methods of manufacture in the field of organic EL devices can be applied to the other parts which are not mentioned here.
  • anode layer 10 shown in Figure 1 is formed from the compounds of group A (group A-1 or group A-2) and group B (group B-1 or group B-2), these inorganic compounds may be used for the cathode layer 16, provided that the work function is less than 4.0 eV.
  • an inorganic thin layer 12 may be omitted inasmuch as the second embodiment is based on the second invention.
  • the anode layer must contain a combination of an inorganic compound of the following group A-1 and a compound of the following group B-1, or a combination of an inorganic compound of the following group A-2 and a compound of the following group B-2. Part of the compounds in the combinations of an inorganic compound of the group A-1 and a compound of the group B-1, and the combinations of an inorganic compound of the group A-2 and a compound of the group B-2 overlap.
  • the combined use of the inorganic compound of group A-1 and the compound of group B-1, or the combined use of the inorganic compound of group A-2 and the compound of group B-2 as an anode layer may produce an organic EL device exhibiting excellent durability and transparency, a low driving voltage (a low specific resistance), and high luminous brightness.
  • the compounds in the combination of the inorganic compound of group A-1 and the compound of group B-1, or the combination of the inorganic compound of group A-2 and the compound of group B-2 excel in etching characteristics when etched using an acid, for example, hydrochloric acid or oxalic acid.
  • Such compounds produce a smooth cross-section in the interface of an acid treated area and a non-treated area, enabling a clear distinction between acid treated areas and non-treated areas. Therefore, the electrode layer made from such inorganic compounds may produce electrode patterns with excellent etching precision and is free from breakage, deformation, and an increase in resistance, even if the electrode is very small or the configuration is complex.
  • inorganic compounds of group A-1 are SiO x (1 ⁇ x ⁇ 2), GeO x (1 ⁇ x ⁇ 2), SnO 2 , PbO, In 2 O 3 , ZnO, GaO, CdO, ZnS, ZnCe, CdSe, In x Zn y O ( 0.2 ⁇ x/(x+y) ⁇ 0.95 ), ZnOS, CdZnO, CdZnS, MgInO, CdInO, MgZnO, GaN, InGaN, MgZnSSe, LiO x (1 ⁇ x ⁇ 2), SrO, CsO x (1 ⁇ x ⁇ 2), CaO, NaO x (1 ⁇ x ⁇ 2), and the like
  • the inorganic compound of group A-2 the inorganic compound of group A-1, excluding SiO x (1 ⁇ x ⁇ 2), can be given.
  • ZnO means oxides of Zn
  • ZnS means sulfides of Zn, wherein the ratio of Zn and O or Zn and S is not necessarily 1:1, but any other ratios are acceptable.
  • inorganic compounds of group A-1 and group A-2 chalcogenides of Sn, In or Zn, and a nitride thereof are preferable.
  • chalcogenides of Sn, In or Zn, and a nitride thereof are preferable.
  • the reason is that, as partly mentioned above, because these inorganic compounds of group A-1 and group A-2 have a small absorption coefficient, particularly small light-quenching characteristics, and superior transparency, it is possible to increase the amount of light which can be emitted out.
  • the inorganic compounds of group A-1 and group A-2 chalcogenides consisting of a combination of In and Zn are particularly preferable. The reason is that the inorganic compound which contains this combination is non-crystalline, and not only has excellent etching characteristics or pattern characteristics, but also may produce an inorganic thin layer with excellent evenness.
  • chalcogenide compounds of Ge Sn, Zn, or Cd
  • oxides are particularly preferable.
  • group A-1 compounds containing at least either In or Zn are desirable.
  • RuO x (1 ⁇ x ⁇ 2), ReO x (1 ⁇ x ⁇ 2), V 2 O 5 , MoO 3 , PdO 2 , Ir 2 O 3 , RhO 4 , CrO 3 , Cr 2 O 3 , MoO x (1 ⁇ x ⁇ 2), WO x (1 ⁇ x ⁇ 2), CrO x (1 ⁇ x ⁇ 2), Nb 2 O 5 , NbO x (1 ⁇ x ⁇ 2), PdO x (1 ⁇ x ⁇ 2), and C (carbon) can be given.
  • These compounds may be used either individually or in combination of two or more.
  • group B-2 in addition to the compounds of group B-1, SiO, SiO 2 , SiON, or SiN x (1 ⁇ x ⁇ 3/2), and the like can be given. These compounds may be used either individually or in combination of two or more.
  • oxides of Ru, Re, V, Mo, Pd, and Ir specifically, RuO x (1 ⁇ x ⁇ 2), ReO x (1 ⁇ x ⁇ 2), V 2 O 5 , MoO 3 , PdO 2 , and Ir 2 O 3 are preferable. As partly mentioned above, it is possible to efficiently increase the ionization potential in the anode layer by using these inorganic compounds.
  • compounds containing Pd are particularly preferable among the compounds of group B-1 and group B-2.
  • a maximum ionization potential may be obtained if the anode layer contains Pd.
  • a chalcogenide of Si or a nitride thereof is not included in the compound of group A-2, it is desirable to select a chalcogenide of Si or a nitride thereof as the compound of group B-2.
  • the content of the group B compounds (compounds of group B-1 or group B-2 may be simply called "group B compounds) will be explained.
  • the content of the group B compound is preferable in the range of 0.5 to 30 atomic % for 100 atomic % of the total of the anode layer. If the content of the group B compound is less than 0.5 atomic %, it may be difficult to adjust the ionization potential of the anode layer to the range of 5.40 to 5.70 eV. On the other hand, if the content of the group B compound is more than 30 atomic %, the anode layer may have a low conductivity, may be colored, or may exhibit impaired transparency (light transmittance).
  • the content of the group B compound is preferably in the range of 0.8 to 20 atomic %, and more preferably 1 to 10 atomic %, for 100 atomic % of the total of the anode layer.
  • the content of the group A compounds (compounds of group A-1 or group A-2 may be simply called "group A compounds) is the total of the anode layer (100 atomic %) minus the content of the group B compounds when the anode layer is made from the group A compounds (group A-1 or group A-2) and the group B compounds (group B-1 or group B-2). Therefore, when the content of the group B compounds is 0.5 to 30 atomic %, the content of the group A compounds is in the range of 70 to 99.5 atomic %.
  • the thickness of the anode layer is not specifically restricted, such a thickness is preferably in the range of 0.5 to 1,000 nm.
  • the thickness of the anode layer is less than 0.5 nm, pin-holes may be produced and a leakage current may be observed when the layer is used for a long period of time; if more than 1,000 nm, on the other hand, transparency of the electrode may be impaired, resulting in low luminous brightness.
  • the thickness of the anode layer is more preferably in the range of 1 to 800 nm, and still more preferably 2 to 300 nm.
  • anode layer there is no specific limitation to the configuration of the anode layer. Either a mono-layer configuration or a multi-layer (two or more layers) configuration is acceptable. Therefore, if high transparency (high light transmittance) and high conductivity is desired, a double layer structure consisting of laminated layers such as a layer of ITO, In 2 O 3 -ZnO, or InZnO, or a metal layer, for example, is preferable.
  • the specific resistance of the anode layer is preferably less than 1 ⁇ cm, for example. If the specific resistance is 1 ⁇ cm or more, not only may the luminosity inside the pixels become uneven, but also the driving voltage of the organic EL device may increase. Therefore, to achieve a low driving voltage, the specific resistance of the anode layer is preferably 40 m ⁇ ⁇ cm or less, and more preferably 1 m ⁇ cm or less.
  • the specific resistance of the anode layer can be determined from a surface resistance measurement using a four probe method resistance measurement apparatus and a thickness which is separately measured.
  • a sputtering method vapor deposition method, spin coat method, sol-gel method by means of casting, spray pyrolysis method, ion-plating method, and the like can be employed.
  • a radio frequency magnetron sputtering method is particularly preferred.
  • sputtering conditions of a vacuum degree of 1 ⁇ 10 -7 to 1 ⁇ 10 -3 Pa, a layer forming speed of 0.01 to 50 nm/second, and a substrate temperature of -50°C to 300°C are preferable.
  • FIG. 2 shows a sectional view of an organic EL device 104 of the third embodiment formed by successively laminating an anode layer 10, an inorganic thin layer 12, a positive hole transport layer 13, an organic light-emitting layer 14, and a cathode layer 16 on a substrate (not shown in the drawing).
  • Injected positive holes may be effectively transported by providing the positive hole transport layer 13. Therefore, transfer of positive holes to the organic light-emitting layer becomes easy and high-speed response of the organic EL device is ensured by providing the positive hole transport layer 13.
  • the organic EL device 104 of the third embodiment shown in Figure 2 has the same configuration as the organic EL device 102 of the first and the second embodiments, except for the insertion of the positive hole transport layer 13 between the inorganic thin layer 12 and the organic light-emitting layer 14. Accordingly, the following description is focused on the positive hole transport layer 13 which is characteristic of the third embodiment.
  • Other parts such as the anode layer 16, the organic light-emitting layer 14, and the like are the same as those in the first and the second embodiments.
  • the positive hole transport layer is preferably formed from an organic compound or an inorganic compound.
  • an organic compound phthalocyanine compounds, diamine compounds, diamine-containing oligomers, thiophene-containing oligomers, and the like can be given.
  • desirable inorganic compounds amorphous silicon ( ⁇ -Si), ⁇ -SiC, microcrystal silicon ( ⁇ C-Si), ⁇ C-SiC, group II-VI compounds, group III-V compounds, amorphous carbon, crystalline carbon, diamond, and the like can be given.
  • the positive hole transport layer is not limited to a mono-layer, but may be a double or triple layer. Although the thickness of the positive hole transport layer is not specifically restricted, this thickness is preferably in the range of 0.5 nm to 5 ⁇ m, for example.
  • Figure 3 shows a sectional view of an organic EL device 106 of the fourth embodiment formed by successively laminating an anode layer 10, an inorganic thin layer 12, a positive hole transport layer 13, an organic light-emitting layer 14, and an electron injection layer 15 on a substrate (not shown in the drawing).
  • Electrons may be effectively injected by providing the electron injection layer 15. Therefore, transferring electrons to the organic light-emitting layer 14 becomes easy, and high-speed response of the organic EL device may be ensured by providing the electron injection layer 15.
  • the organic EL device 106 of the fourth embodiment shown in Figure 3 has the same configuration as the organic EL device 104 of the third embodiment, except for the insertion of the electron injection layer 15 between the organic light-emitting layer 14 and the cathode layer 16. Accordingly, the following description is focused on the electron injection layer 15 which is characteristic of the fourth embodiment.
  • Other parts are the same as those in the first to the third embodiments or the configurations known in the field of organic EL devices.
  • the electron injection layer is preferably formed from an organic compound or an inorganic compound.
  • the use of an inorganic compound produces organic EL devices with better electron injection performance from a cathode layer and superior durability.
  • 8-hydroxyquinoline As preferable organic compounds, 8-hydroxyquinoline, oxadizole, and derivatives of these compounds, such as a metal chelate oxynoide compound containing 8-hydroxyquinoline, can be given.
  • An insulating material or semiconductor are preferably used as an inorganic compound forming the electron injection layer. If the electron injection layer is made from an insulator or a semiconductor, leakage of current may be effectively prevented, resulting in improvement in electron injection performance.
  • One or more metal compounds selected from the group consisting of alkali metal chalcogenides (oxides, sulfides, selenides, tellurides), alkaline earth metal chalcogenides, alkali metal halides, and alkaline earth metal halides can be used as such an insulator. If the electron injection layer is made from these alkali metal chalcogenides or the like, electron injection performance may be further improved.
  • preferable alkali metal chalcogenides Li 2 O, LiO, Na 2 S, Na 2 Se, and NaO can be given.
  • preferable alkaline earth metal chalcogenides for example, CaO, BaO, SrO, BeO, BaS, and CaSe can be given.
  • LiF, NaF, KF, LiCl, NaCl, KCl, NaCl, and the like can be given as examples of preferable alkali metal halides.
  • fluorides such as CaF 2 , BaF 2 , SrF 2 , MgF 2 , and BeF 2 , and halides other than fluorides can be given.
  • oxides, nitrides, and oxynitrides containing at least one element selected from Ba, Ca, Sr, Yb, Al, Ga, In, Li, Na, Cd, Mg, Si, Ta, Sb, and Zn can be given. These compounds can be used either individually or in combination of two or more.
  • the inorganic compounds forming the electron injection layer are preferably in the form of a microcrystalline or amorphous insulating thin layer. If the electron injection layer is formed from these insulating thin layer, pixel deficiencies such as dark spots and the like may be reduced because a uniform and homogeneous thin layer for the electron injection layer may be obtained from these insulating thin layer.
  • alkali metal chalcogenides As such an inorganic compound, the above-mentioned alkali metal chalcogenides, alkaline earth metal chalcogenides, alkali metal halides, and alkaline earth metal halides can be given.
  • the electron injection layer may be made from a known organic compound having electron transport characteristics, or a mixture of such an organic compound and an alkali metal, for example, a mixture of the above-mentioned metal chelate compound containing 8-hydroxyquilyl (Alq) and Cs.
  • the electron affinity of the electron injection layer in the first embodiment is in the range of 1.8 to 3.6 eV. If the electron affinity is less than 1.8 eV, electron injection performance decreases and the driving voltage increases, resulting in a lowered luminous efficiency; if the electron affinity is more than 3.6 eV, a complex with a low luminous efficiency tends to be produced and a blocking junction may occur.
  • More preferable range of the electron affinity of the electron injection layer is therefore from 1.9 to 3 eV, and the range from 2 to 2.5 eV is ideal.
  • the difference between the electron affinity of the electron injection layer and that of the organic light-emitting layer be 1.2 eV or less, and more preferably 0.5 eV or less.
  • the smaller the difference in the electron affinity the easier the electron injection from the electron injection layer into the organic light-emitting layer, ensuring a high-speed response of the organic EL device.
  • the energy gap (bandgap energy) of the electron injection layer in the first embodiment be 2.7 eV or more, and more preferably 3.0 eV or more.
  • the energy gap is greater than a prescribed value, 2.7 eV or more for example, positive holes move to the electronic injection layer through an organic light-emitting layer only with difficulty.
  • the recombining efficiency of positive holes and electrons is thus improved, resulting in an increase in the luminous brightness of the organic EL device and avoiding the case in which the electron injection layer itself emits light.
  • the configuration of the electron injection layer made from an inorganic compound will be described.
  • the configuration of the electron injection layer Either a mono-layer configuration or a multi-layer (two or more layers) configuration is acceptable.
  • the thickness of the electron injection layer is not specifically restricted, this thickness is preferably in the range of 0.1 nm to 1,000 nm, for example. If the thickness of the electron injection layer made from an inorganic compound is less than 0.1 nm, the electron injection force may decrease or the mechanical strength may be impaired. If the thickness of the electron injection layer made from an inorganic compound is more than 1,000 nm, resistance is too high so that it may be difficult for the organic EL device to exhibit a high-speed response and may take a long time to form the layers. Therefore, the thickness of the electron injection layer made from an inorganic compound is more preferably from 0.5 to 100 nm, and still more preferably from 1 to 50 nm.
  • the method of forming the electron injection layer is not specifically limited inasmuch as a thin layer with a uniform thickness is obtained.
  • a vacuum deposition method, spin coating method, casting method, LB method, sputtering method, and the like can be employed.
  • a fifth embodiment of the present invention will be explained with reference to Figures 4 to 6.
  • the method of the fifth embodiment ensures production of a thin inorganic layer with a uniform ratio of components even if a plurality of inorganic compounds is used. This consequently provides efficient method of manufacture of organic EL devices exhibiting high luminous brightness at a low driving voltage and having excellent durability.
  • a first feature of the fifth embodiment is forming an inorganic thin layer by using a specific target and a radio frequency magnetron sputtering method.
  • a second feature of the fifth embodiment is in the use of a plurality of organic light-emitting materials.
  • an organic light-emitting layer with a uniform ratio of components may be obtained by using a plurality of organic light-emitting materials and a rotation vapor deposition method.
  • Such an organic light-emitting layer ensures efficient manufacture of organic EL devices exhibiting high luminous brightness at a low driving voltage, and having excellent durability.
  • a third feature of the fifth embodiment is providing a vacuum vessel for the radio frequency magnetron sputtering operation and another vacuum vessel for the vacuum deposition operation, and connecting the two vacuum vessels in advance for a continuous operation, wherein, after the vacuum deposition operation, the material is transferred to the vacuum vessel for the radio frequency magnetron sputtering method using a carriage means.
  • the organic EL device with the same configuration as that used in the fourth embodiment is used for convenience.
  • the following layers are prepared using the manufacturing method of the fifth embodiment.
  • the method of manufacturing each layer is as follows.
  • anode layer and an inorganic thin layer using the radio frequency magnetron sputtering method it is desirable to use a target which consists of the inorganic compounds of group A and group B.
  • the target contains at least the inorganic compounds of group A and group B in a prescribed ratio, and is preferably prepared by homogeneously mixing the raw materials (average particles diameter: 1 ⁇ m) using a solution method (a coprecipitation method) (concentration: 0.01 to 10 mol/l, solvent: polyhydric alcohol, etc., precipitation agent: potassium hydroxide, etc.) or a physical mixing method (stirrer: a ball mill, bead mil, etc., mixing time: 1 to 200 hours), followed by sintering (temperature: 1,200 to 1,500°C, time: 10 to 72 hours, preferably, 24 to 48 hours) and molding (press molding, HIP molding, etc.).
  • a solution method a coprecipitation method
  • a physical mixing method stirrrer: a ball mill, bead mil, etc., mixing time: 1 to 200 hours
  • the targets obtained by these methods have uniform characteristics.
  • the preferable temperature is raised at a rate of 1 to 50°C per minute.
  • the inorganic compounds of group A and group B can also be sputtered separately.
  • radio frequency magnetron sputtering is preferably performed in an inert gas such as argon under vacuum of 1 ⁇ 10 -7 to 1 ⁇ 10 -3 Pa, a layer forming speed of 0.01 to 50 nm/second, and a substrate temperature of -50°C to 300°C. These conditions of sputtering ensures production of an inorganic thin layer having a precise and uniform thickness.
  • the method using a vacuum deposition apparatus 201 is characterized by providing a rotation axis line 213A passing through the geometrical center of the substrate 203 around which it is rotated, arranging vapor deposition material containers 212A to 212F at positions apart from the rotation axis line 213A of the substrate 203, and causing the different vapor deposition materials to simultaneously vaporize from the vapor deposition material containers 212A to 212F arranged opposingly to the substrate 203 while rotating the substrate 203 around a rotation axis 213.
  • the vacuum deposition apparatus 201 shown in Figures 4 and 5 has a vacuum vessel 210, a substrate holder 211 installed in the upper portion of the vacuum vessel 210 for securing the substrate 203, and a plurality of (six) vapor deposition material containers 212A to 212F for filling vapor deposition materials, which are opposingly arranged below the substrate holder 211.
  • This vacuum vessel 210 is designed so that an exhaust means (not shown in the drawing) can maintain the internal pressure at a prescribed reduced pressure.
  • six vapor deposition materials are shown in the drawing, the number is not necessarily limited to six. Five or less or seven or more materials are acceptable.
  • the substrate holder 211 has a holder section 215 which supports the peripheral portion of the substrate 203 and holds the substrate 203 horizontally in the vacuum vessel 210.
  • a rotation axis member 213 for rotating the substrate 203 is provided in the vertical direction upwardly in the center of the substrate holder 211.
  • a motor 214 which is a rotation driving means is connected to the rotation axis member 213.
  • the substrate 203 held in the substrate holder 211 is rotated together with the substrate holder 211 around the rotation axis member 213 by the rotational movement action of the motor 214.
  • the rotation axis line 213A extending from the rotation axis member 213 is set in the vertical direction in the center of the substrate 203.
  • a square substrate 203 shown in Figure 5 is caused to engage the holding section 215 of the substrate holder 211 and is horizontally maintained.
  • the host material and doping material are filled into each of the two vapor deposition material containers 212B and 212C which are located in juxtaposition on a virtual circle 221 shown in Figure 4, and pressure in the vacuum vessel 210 is reduced to a vacuum of a prescribed level, 1.0 ⁇ 10 -4 Torr (133 ⁇ 10 -4 Pa), for example, using an exhaust means.
  • the vapor deposition material containers 212B and 212C are heated to cause the host material, and doping material to simultaneously vaporize from the respective containers.
  • a motor 214 is driven to rotate the substrate 203 at a prescribed rate, 1 to 100 rpm (revolution per minute) for example, around the rotation axis line 213A.
  • the organic light-emitting layer 12 is formed by causing the host material and doping material to deposit while rotating the substrate 203 in this manner.
  • the vapor deposition material containers 212B and 212C are provided in the positions at a prescribed distance "M" from the rotation axis line 213A of the substrate 203 in the horizontal direction as shown in the Figure 5, it is possible to regularly change the angle of incidence to the substrate 203 of the vapor deposition materials such as the host material and doping material by rotating the substrate 203.
  • to revolve a substrate means to cause the substrate to rotate around an axis which is some distance from its geometric center. This requires a larger space than the case where the substrate rotates around its geometrical center.
  • the substrate 203 there are no specific limitations to the configuration of the substrate 203 in carrying out the simultaneous vapor deposition.
  • the substrate 203 is a plate as shown in Figure 4, for example, it is desirable to arrange a plurality of vapor deposition material containers 212A to 212F along the perimeter of a virtual circle 221 around the rotation axis line 213A of the substrate 203, so that the relationship " M > (1/2) ⁇ L " is satisfied, wherein "M” is the diameter of the virtual circle 221 and “L” is the length of one side of the substrate 203.
  • "L" indicates the length of the longest side.
  • This arrangement ensures easy control of the compositional ratio of the vapor deposition materials because the vapor deposition materials from a plurality of containers 212A to 212F become attached to the substrate 203 at the same angle of incidence.
  • this arrangement ensures vaporization of the vapor deposition materials at a certain angle of incidence to the substrate 203 and prevent the vapor deposition materials from evaporating at right angles, uniformity of the compositional ratio in the formed layer may be further improved.
  • a plurality of vapor deposition material containers 212A to 212F is arranged along the perimeter of a virtual circle 221 around the rotation axis line 213A of the substrate 203 as shown in Figure 4.
  • the vapor deposition material containers 212A to 212F are arranged with an angle of 360°/n from the center of the virtual circle 221, wherein "n" indicates the number of vapor deposition material containers.
  • n indicates the number of vapor deposition material containers.
  • a thin layer (an electronic injection layer) with a thickness of 1,000 ⁇ (a prescribed value) is prepared by simultaneous vapor deposition using Alq as a host material and Cs as a doping material while rotating the substrate 203 shown in Figure 6 at 5 rpm under the following conditions.
  • Cs is used here to increase the electronic conduction of Alq, not as a conventional doping agent to emit light.
  • the following example is given as a typical method of forming uniform layer. Although Cs itself has no light-emitting function, the example is applicable when Cs is replaced with a doping agent with a light-emitting function.
  • the thickness of the resulting thin layer at measuring points (4A to 4M) on a glass substrate 203 shown in Figure 6 was measured using a tracer-type thickness meter.
  • the composition ratio (the atomic ratio) Cs/Al (Al in Alq) at the above measuring points (4A to 4M) was also measured by using an X-ray photoelectron spectrometer (XPS).
  • XPS X-ray photoelectron spectrometer
  • a thin layer with a thickness of 1,000 ⁇ was prepared under the same vapor deposition conditions as in the above simultaneous vapor deposition, except that the substrate 203 was not rotated.
  • the thickness and atomic ratio Cs/Al (Al in Alq) of the resulting thin layer at measuring points (4A to 4M) were measured.
  • the results are shown in Table 2.
  • Measuring point Thickness ( ⁇ ) Cs/Al 4A 895 0.6 4B 941 1.1 4C 884 1.1 4D 911 0.7 4E 922 1.1 4F 1,022 0.8 4G 919 1.2 4H 1,015 1.3
  • the minimum thickness and the maximum thickness of the layer prepared by the simultaneous vapor deposition method at the measuring points (4A to 4M) on the surface of the substrate 203 were respectively 1,008 ⁇ (100.8 nm) and 1,093 ⁇ (109.3 nm).
  • the layer was confirmed to have a very uniform thickness, with a maximum thickness difference of as small as 85 ⁇ , and also to have a very homogeneous composition, with an atomic ratio Cs/Al within the range of 1.0 to 1.1.
  • the layer prepared by a method differing from the above simultaneous vapor deposition method had a thickness which fluctuated from 884 ⁇ to 1,067 ⁇ at the measuring points (4A to 4M) on the substrate 203.
  • the atomic ratio Cs/Al also showed fluctuations ranging from 0.6 to 1.3.
  • a transparent electrode layer with a thickness of 75 nm was formed from ITO as an anode layer on a transparent glass substrate with a dimension of thickness:1.1 mm ⁇ length:25 mm ⁇ width:75 mm.
  • the glass substrate and the anode layer are collectively called a substrate in the following description.
  • This substrate was ultrasonically washed in isopropyl alcohol, dried in a nitrogen gas atmosphere, and washed for 10 minutes using UV (ultraviolet radiation) and ozone.
  • the substrate on which an anode layer has been formed was placed in a vacuum vessel for common use as a radio frequency sputtering apparatus and a vacuum deposition apparatus.
  • a target consisting of tin oxide and ruthenium oxide (at a ratio of 10:1) to form an inorganic thin layer was installed in the vacuum vessel.
  • a mixed gas of oxygen and argon was introduced.
  • An inorganic thin layer with a thickness of 10 nm was formed by sputtering at an output of 100 W and a substrate temperature of 200°C.
  • the vapor deposition material container 212B was filled with a compound described by the formula (6) (abbreviated as DPVTP) as an organic light-emitting material
  • the container 212C was filled with a compound described by the formula (24) (abbreviated as DPAVBi) as another organic light-emitting material
  • the container 212D was filled with Alq which forms an electronic injection layer
  • the container 212E was filled with a metal (Al) which forms part of a cathode layer
  • the container 212F was filled with another metal (Li) which forms part of the cathode layer.
  • an organic light-emitting layer, an electron injection layer, and a cathode layer were sequentially laminated on the substrate consisting of an anode layer and an inorganic thin layer, thereby obtaining an organic EL device.
  • the same vacuum conditions were constantly maintained all through the operation from formation of the organic light-emitting layer through the formation of the cathode layer.
  • DPVTP and DPAVBi were simultaneously vaporized from the vapor deposition material containers 212B and 212C under the following conditions to form an organic light-emitting layer on an inorganic thin layer.
  • the method of the fifth embodiment was followed in simultaneously depositing vaporized DPVTP and DPAVBi.
  • the vapor deposition material containers 212B and 212C were respectively arranged at positions at a distance from the rotation axis line of the substrate of 30 mm in the horizontal direction, and the containers were heated in this positional arrangement to simultaneously vaporize DPVTP and DPAVBi, while rotating the substrate around the rotation axis at 5 rpm.
  • Alq was vaporized from the vapor deposition material containers 212D under the following conditions to form an An electron injection layer on the organic light-emitting layer.
  • Al and Li were vaporized respectively from the vapor deposition material containers 212E and 212F to form a cathode layer on the electron injection layer, thereby providing an organic EL device.
  • a DC voltage of 8V was applied between the cathode layer (minus (-) electrode) and the anode layer (plus (+) electrode) of the resulting organic EL device.
  • the current density was 1.5 mA/cm 2 and the luminous brightness was 127 nit (cd/m 2 ).
  • the emitted color was confirmed to be blue.
  • durability was evaluated by driving at a constant current of 10 mA/cm 2 , to confirm that there was no occurrence of a leakage current after operating for 1,000 hours and longer.
  • Example 1 2 3 4 Anode layer material ITO ITO ITO ITO ITO Ip(eV) 5.0 5.0 5.0 5.0 Thickness (nm) 75 75 75 75 75 Inorganic thin layer material Sn oxide/Ru oxide SiO x /Ru oxide GeO x /Ru oxide SiO x /Ru oxide (10/1.5) Ip(eV) 5.53 5.53 5.47 5.54 Thickness (nm) 1 2 1 5 Light-emitting layer material DPVTP /DPAVBi DPVTP /DPAVBi DPVTP /DPAVBi DPVTP /DPAVBi Thickness (nm) 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 Electron injection layer material Alq Alq Alq Thickness (nm) 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5
  • Examples 2 to 4 organic EL devices were prepared in the same manner as in Example 1, except for changing the types of inorganic compounds and the amounts of the components as shown in Table 3. Luminous brightness and the like were evaluated.
  • the ionization potential of the inorganic thin layer of each Example was 5.4 eV or more. This is presumed to be due to an intermediate level formed in the inorganic thin layer.
  • the ionization energy of DPVTP which is an organic light-emitting material was 5.9 eV, confirming that the value is greater than the intermediate level (an energy value) of the inorganic thin layer.
  • the organic EL device of Comparative Example 1 was prepared in the same manner as in Example 1, except that an inorganic thin layer was not formed. A DC voltage of 10V was applied to the resulting organic EL device in the same manner as in Example 1. As a result, although the organic EL device emitted blue light, the current density was 2.2 mA/cm 2 and the luminous brightness was 127 nit (cd/m 2 ). In addition, when the organic EL device was operated at a constant current of 10 mA/cm 2 , a leakage current occurred before operating for 1,000 hours and the organic EL device ceased to emit light.
  • the organic EL device of Comparative Example 2 was the same as that of Example 1, except that an inorganic thin layer was formed using only tin oxide.
  • a DC voltage of 10V was applied to the resulting organic EL device in the same manner as in Example 1. This driving voltage was 2V higher than that used in Examples 1 to 4 (8V).
  • the organic EL device emitted blue light, the current density was 0.9 mA/cm 2 and the luminous brightness was 68 nit (cd/m 2 ).
  • the organic EL device was operated at a constant current of 10 mA/cm 2 in the same manner as in Example 1 to confirm that a leakage current did not occur after operating for 1,000 hours.
  • the organic EL device of Comparative Example 3 was the same as that of Example 1, except that an inorganic thin layer was formed using only aluminum nitride.
  • a DC voltage of 10V was applied to the resulting organic EL device in the same manner as in Example 1. This driving voltage was 2V higher than that used in Examples 1 to 4 (8V).
  • the current density was 0.6 mA/cm 2 and the luminous brightness was 20 nit (cd/m 2 ).
  • the organic EL device was operated at a constant current of 10 mA/cm 3 in the same manner as in Example 1 to confirm that a leakage current did not occur after operating for 1,000 hours.
  • Examples 5 to 10 organic EL devices were prepared in the same manner as in Example 1, except for changing the materials for forming anode layers and inorganic thin layers as shown in Table 5. Luminous brightness and the like were evaluated.
  • Example 9 nitrogen gas was added to a mixture of argon gas and oxygen gas. Then the resulting gas mixture was used after plasma-treatment.
  • Example 10 a mixture of argon gas and nitrogen gas was used after plasma-treatment.
  • the results are shown in Table 5, wherein IZO means non-crystalline indium zinc oxide.
  • a mixture of indium oxide powder and iridium oxide powder (average particle diameter: 1 ⁇ m or less) was placed in a wet-type ball, mill in the amounts so that the molar ratio of Ir/(In+Ir) is 0.02 and pulverized for 72 hours.
  • the resulting pulverized material was granulated and press-molded to form a disk with a diameter of 4 inch and a thickness of 5 mm.
  • the disk was sintered at a temperature of 1,400°C for 36 hours to obtain a target 1 for an anode layer.
  • a transparent glass substrate with a dimension of thickness:1.1 mm ⁇ length:25 mm ⁇ width:75 mm and the target 1 were placed in a vacuum vessel for common use as a radio frequency sputtering apparatus and a vacuum deposition apparatus.
  • the radio frequency sputtering apparatus was operated to form a transparent electrode layer with a thickness 75 nm as an anode layer.
  • a mixed gas of oxygen and argon was fed.
  • a transparent electrode layer was formed by sputtering in this atmosphere at an output of 100 W and a substrate temperature of 25°C for 14 minutes.
  • the glass substrate and the anode layer are collectively called a substrate in the following description.
  • This substrate was ultrasonically washed in isopropyl alcohol, dried in a nitrogen gas atmosphere, and washed for 10 minutes using UV (ultraviolet radiation) and ozone.
  • the ionization potential of the anode layer in the substrate was measured using "AC-1" (Riken Instrument Co., Ltd.) to find that ionization potential was 5.54 eV.
  • the light transmittance (wavelength 550 nm) of the substrate from which the anode layer was formed was measured to confirm that the light transmittance was 80%.
  • the substrate on which an anode layer has been formed was placed in a vacuum vessel for common use as a radio frequency sputtering apparatus and a vacuum deposition apparatus.
  • a target 2 consisting of tin oxide and ruthenium oxide was installed in the vacuum vessel.
  • an inorganic thin layer with a thickness of 10 nm was formed by sputtering at an output of 100 W and a substrate temperature of 200°C.
  • the vapor deposition material container 212B was filled with a compound DPVTP which forms part of an organic light-emitting layer
  • the container 212C was filled with DPAVBi which is another compound forming the organic light-emitting layer
  • the container 212D was filled with an organic compound Alq which forms an electronic injection layer
  • the container 212E was filled with a metal (Al) which forms part of a cathode layer
  • the container 212F was filled with another metal (Li) which forms part of the cathode layer.
  • an organic light-emitting layer, an electron injection layer, and a cathode layer were sequentially laminated on the substrate consisting of an anode layer and an inorganic thin layer, thereby obtaining an organic EL device.
  • the method of the fourth embodiment was followed in carrying out the simultaneous deposition.
  • the vapor deposition material containers 212B and 212C were respectively arranged at positions apart from the rotation axis line of the substrate by 30 mm in the horizontal directions, and the containers were heated in this positional arrangement to simultaneously vaporize DPVTP and DPAVBi, while rotating the substrate around a rotation axis at 5 rpm.
  • Alq was vaporized from the vapor deposition material containers 212D under the following conditions to form an electron injection layer on the organic light-emitting layer.
  • Al and Li were vaporized respectively from the vapor deposition material containers 212E and 212F to form a cathode layer on the electron injection layer, thereby obtaining an organic EL device.
  • a DC voltage of 8V was applied between the cathode layer (minus (-) electrode) and the anode layer (plus (+) electrode) of the resulting organic EL device.
  • the current density was 1.1 m/cm 2 and the luminous brightness was 89 nit (cd/m 2 ).
  • the emitted color was confirmed to be blue.
  • durability was evaluated by driving at a constant current of 10 mA/cm 2 , to find that there was no occurrence of a leakage current after the operation of 1,000 hours and longer. The results are shown in Table 6.
  • the ionization potential of the anode layer was 5.46 eV.
  • a DC voltage of 8V was applied to the resulting organic EL device between the electrodes to confirm that the current density was 1.4 mA/cm 2 and the luminous brightness was 108 nit (cd/m 2 ). In addition, the emitted color was confirmed to be blue.
  • the ionization potential of the anode layer was 5.60 eV.
  • Example 11 In the same manner as in Example 11, a DC voltage of 8V was applied to the resulting organic EL device between the electrodes to confirm that the current density was 1.4 mA/cm 2 and the luminous brightness was 108 nit (cd/m 2 ). In addition, the emitted color was confirmed to be blue.
  • the ionization potential of the anode layer was 5.52 eV.
  • Example 11 In the same manner as in Example 11, a DC voltage of 8V was applied to the resulting organic EL device between the electrodes to confirm that the current density was 1.2 mA/cm 2 and the luminous brightness was 94 nit (cd/m 2 ). In addition, the emitted color was confirmed to be blue.
  • Organic EL devices were prepared in the same manner as in Example 11, except for using the targets shown in Table 7 instead of the target 1 in Example 11, the compound described by the formula (8) (hereinafter abbreviated as DPVDPAN) as an light-emitting layer material, and the compound described by the formula (23) (hereinafter abbreviated as PAVB) as a doping material to be added to the light-emitting layer.
  • DPVDPAN the compound described by the formula (8)
  • PAVB compound described by the formula (23)
  • the surface roughness of the anode layers was measured by using a surface roughness meter to confirm that the mean value of the squares was less than 10 nm, confirming that the surfaces were and very smooth.
  • Example 20 which is a mixture of crystals and amorphous materials, exhibited surface roughness of less than 35 nm.
  • the anode partly short-circuited, although a current could flow at a low voltage.
  • A indicates the number of mols of the anode layer material (indium oxide) in the first row
  • B indicates the number of mols of the anode layer material (zinc oxide) in the second row
  • C indicates the number of mols of the anode layer material (palladium oxide) in the third row.
  • the ionization potential of the anode layer was 5.52 eV.
  • Example 11 In the same manner as in Example 11, a DC voltage of 8V was applied to the resulting organic EL device between the electrodes to confirm that the current density was 1.2 mA/cm 2 and the luminous brightness was 95 nit (cd/m 2 ). In addition, the emitted color was confirmed to be blue.
  • the ionization potential of the anode layer was 5.45 eV.
  • Example 11 In the same manner as in Example 11, a DC voltage of 8V was applied to the resulting organic EL device between the electrodes to confirm that the current density was 1.1 mA/cm 2 and the luminous brightness was 84 nit (cd/m 2 ). In addition, the emitted color was confirmed to be blue.
  • the ionization potential of the anode layer was 5.49 eV.
  • Example 11 In the same manner as in Example 11, a DC voltage of 8V was applied to the resulting organic EL device between the electrodes to confirm that the current density was 1.2 mA/cm 2 and the luminous brightness was 93 nit (cd/m 2 ). In addition, the emitted color was confirmed to be blue.
  • the ionization potential of the anode layer was 5.31 eV.
  • Example 11 In the same manner as in Example 11, a DC voltage of 8V was applied to the resulting organic EL device between the electrodes to confirm that the current density was 1.4 mA/cm 2 and the luminous brightness was 120 nit (cd/m 2 ). In addition, the emitted color was confirmed to be blue.
  • the ionization potential of the anode layer was 5.26 eV.
  • Example 11 In the same manner as in Example 11, a DC voltage of 8V was applied to the resulting organic EL device between the electrodes to confirm that the current density was 1.1 mA/cm 2 and the luminous brightness was 90 nit (cd/m 2 ). In addition, the emitted color was confirmed to be blue.
  • the ionization potential of the anode layer was 5.30 eV.
  • Example 11 In the same manner as in Example 11, a DC voltage of 8V was applied to the resulting organic EL device between the electrodes to confirm that the current density was 2.4 mA/cm 2 and the luminous brightness was 190 nit (cd/m 2 ). In addition, the emitted color was confirmed to be blue.
  • the ionization potential of the anode layer was 5.23 eV.
  • Example 11 In the same manner as in Example 11, a DC voltage of 8V was applied to the resulting organic EL device between the electrodes to confirm that the current density was 0.6 mA/cm 2 and the luminous brightness was 49 nit (cd/m 2 ). In addition, the emitted color was confirmed to be blue.
  • an intermediate level for injection of electron charges may be formed in the inorganic thin layer without using a tunnel effect by forming the inorganic thin layer by a combination of several specific inorganic compounds, for example. Therefore, the present invention provides an organic EL device exhibiting superior durability, a low driving voltage, and high luminous brightness, and method of efficiently manufacturing such an organic EL device.
EP00902980A 1999-02-15 2000-02-15 Organische elektrolumineszente vorrichtung und verfahren zu ihrer herstellung Withdrawn EP1083776A4 (de)

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JP11036420A JP2000235893A (ja) 1999-02-15 1999-02-15 有機エレクトロルミネッセンス素子およびその製造方法
JP3642199 1999-02-15
JP3642099 1999-02-15
JP3642199 1999-02-15
JP13499799A JP4673947B2 (ja) 1999-02-15 1999-05-14 有機エレクトロルミネッセンス素子およびその製造方法
JP13499799 1999-05-14
PCT/JP2000/000832 WO2000048431A1 (fr) 1999-02-15 2000-02-15 Dispositif organique electroluminescent et son procede de fabrication

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CN1294834A (zh) 2001-05-09
US6635365B2 (en) 2003-10-21
WO2000048431A1 (fr) 2000-08-17
EP1083776A4 (de) 2003-10-15
KR20010042727A (ko) 2001-05-25
US6416888B1 (en) 2002-07-09
CN100382354C (zh) 2008-04-16
US20020155319A1 (en) 2002-10-24
KR100702763B1 (ko) 2007-04-03

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